Manufacture of derivatives of toluene.



UNITED STATES PATENT OFFICE.

J'ULES MAIRE, OF ABGENTEUIL, FRANCE, ASSIGNOB TO ALPHONSE EMILE VEBGE, OF

VINCENNES, FRANCE- MANUFAGTURE OF DERIVATIVES 'OF TOLUENE.

To all whom it may concern:

ing at Argenteuil, France, have invented a new and useful Improvement in the Manufacture of Derivatives of Toluene, which is fully set forth in the following specification.

In recent years, it has been attempted to remedy the defects of gelatin explosives containing nitroglycerin, by substituting for the latter, either partly or wholly, various liquid nitro-compounds which are also solvents of nitro-cellulose, the chief object of this substitution being to obtain gelatins which freeze at a lower temperature than gelatin dynamites. More particularly, it for the purpose specified,. liquid nitro-to uene compounds which recently appeared in the market un-,

der the name of liquid trinitro-toluenes, but the gelatin explosives thus obtained have not fulfilled expectations, since, after having been stored for a certain time, they gradually harden and freeze more and more easily, this being due to the fact that the said liquid trinitro-toluenes are products which are not properly defined and are essentially variable not only if obtained from different factories, but also if obtained at different times from the same factory. These liquid trinitro-toluenes vary materially as regards the proportion of nitrogen,

(from 14.5 to 15.8 per cent), and the freezing point, (from --5 C. to 20 C.). They remain in a state of very pronounced superfusion for several weeks after their manufacture, then become muddy, thickened and changed in color. They .all have a more or less pronounced smell of mononitro-toluene, and lose a considerable fraction of their weight after having been heated for a short time to (3., (from 2 to 2.5 per cent. at the end of twenty-four :hours). During heating, they precipitate more or low considerable uantities of solid matter. It follows, there om, that gelatin explosives manufactured with these pseudo-liquids, are completely modified after having been heated; that is to say, they lose their plasticity and become hardened, while the smell is not changed. Also it may be pointed out, in passing, that this partial volatilization, shown and accelerated by the heating, necessarily takes place at the ordinary tempflrature -i.n course of time, so that Specification of Letters Yatent.

Application filed-July 21, 19,18. fieriatlio. 780,836.

Patented Jan. 12, 1915.

the aforesaid compounds are obviously, therefore, merely by-products of undetermined compos tion, obtained by chance in the course of manufacture, in which the subsequent addition of liquid mononitrotoluene enables the solid trinitro-toluene to be artificially dissolved, so as to increase the proportion of nitrogen. The spontaneous volatiliza-tion of the mononitro-toluone, which is inevitable in the course of tlme, results, as has been shown, in the crystallizatlon of the solid products which are dlssolvedby its means, and thus also read- 11y explains the progressive hardening of the gelatin explosives obtained with these pseudo-liquids, during their storage. Moreover, this hardening is unavoidable after a lapse of a few weeks, even in a closed vessel, owing .to the spontaneous cessation of the state of super-fusion which characterizestheseQpseudo-liquids.

This invention relates to the systematic manufacture of new supernitrated compounds .of toluene which, on the contrary, are true liquids, inasmuch as they have sharply defined melting points which can be accurately determined almost within 1, and if they are \cooled, they no longer precipita-te solid material but are entirely frozen. They are all odorless, and lose only a very small proportion of their weight when heated to 60 (1., their properties continuing unmodified after such heating, and the compounds themselves remaining as clear .as ever. Gelatin explosives manufactuned with these liquids do not show any change in plasticity after heating, but remain plastic no matter .how long they may be stored.

An. entire series of liquid nitro-toluenes complying with the different conditions and containing proportions of nitrogen between 15.3 and 1.6 per cent, and melting between the ordinary temperature and -20 C. can be obtained in accordance by the methods hereinafter described.

Up- .to the present time, generally speaking, all .nitro-toluenes, whether simple or complex, .solid or pseudo-liquid, having a degree of nitration greater than that of mononitro-toluene, have been obtained by starting operations either with para-mononitro-toluene alone, or with ortho-mononitro-toluene alone, or with :a more or less defined mixture of both and meta-monohas heretofore been done, the proportion of meta-'mononitro toluene is always very con siderable and varles between a mmlmurn of 45 percent, and a maximum of 85 per cent.,

the "remainder being constituted either by ortho-mononitro-toluene, or by para-mononitro-toluenes in which, contrary to what using smaller proportions of meta-mononitro-toluene than the said minimum, or

greater than the said maximum, only solid or pasty products are obtained.

Liquid compounds which'are exactly binitrated and which form what will be called Series I',-areiobtained by mixing with the usual nitrating mixtures of sulfuric and nitric acids, mixtures of mononitro-toluenes constituted in accordance with the principle above referred to. .They are also obtained by mixing with the desired quantity of binitro-toluene'obtained by. the nitration of meta-mononitro toluene, suitable quantities of binitro-toluenes. obtained by nitration either of ortho mononitro-toluene alone, or of para-mononitro-toluene alone, or of a mixture ofboth, the transformation of the mixture of mononitro-toluenes into binitrotoluenes being. effected with the aid of any of the nitrating mixtures generally used for this operation.

Supernitrated liquid compounds, forming what may be called Series II, are obtained in turn by any of the following methods, the first and simplest of which consists in dissolving one of liquid'binitro-toluenes of Series I, in a definite quantity of pure solid trinitro-toluene, (melting point 82 (3.), or of commercially solid trinitro-toluene (melting point from to 72 0.). The second method consists in nitrating with the usual nitrating mixtures, binitro-toluenes of Series I, and then dissolving a definite quantity of the trinitr0-toluenes thus obtained in any one of the liquid binitro-toluenes of Series I. The third method, which is more complicated consists in subjecting to the action of the usual nitrating mixtures, a mixture of given proportions of solid trinitro-toluene with meta-mononitro-toluene, to which latter have been previously added dissolved quantities of either ortho-mononitro-toluene or, paramononitro-toluene, or both, as previously stated. (It is obvious that in the latter case the trinitro-derivative does not take part in the nitration, and that at the moment of the usual washing terminating the operation, there is a risk of a portion of the same being dissolved in the washing water to the detri ment of the final proportion of nitrogen.) It is also possible, as a fourth method, to subject the mixture in desired proportions of meta-mononitro-toluene and either the ortho-mononitro-toluene or para-mononitrotoluene, or both, to the nitrating action of such a quantity of .the nitrating mixture, and in such conditions of temperature, as to produce at once not only binitro-toluene, but, also, the desired proportion of binitrotoluene, in order to obtain the desired supernitrated derivatives in liquid form. This method is, however, more difiicult than the preceding ones, as it requires a higher temperature for the nitration, and the yield is less good, owing'to unavoidable losses by oxidation. Itis obvious that it would be also possible to employ other more or less indirect methods, but in all of these cases, the common and indispensable feature, is, as may be seen, the use at the beginning of the operation or operations, of a very considerable proportion of meta-mononitro-toluene combined with the use, equally imperative, of large quantities of ortho-mononitrotoluene, or of para-mononitro-toluene, or of a mixture of both, the proportion of the meta-mononitro-toluene which must remain between 4.5 and per cent. of the whole, varying according to the method adopted and according to the liquid compound to be obtained;

Examples of the relative proportions of the diiferent ingredients used in various cases for obtaining given liquid compounds are given below:

(1) Production of liquid derivatives exactly binitrated, (Series I).

' (a) Use of meta-mononitro-toluene with ortho-mononitro-toluene alone.

(6) Use of the meta-mononitro-toluene and of the para-mononitro-toluene.

Meta- Paramcuonitromononitro- Freezing point.

toluene. toluene. I

Parts. Parts 85 15' Solid at ordinary temperatures. 80 20 -"2. 70 30 -6. 65 35 Solid at ordinary temperatures;

(0) Use of the meta-mononitro-toluene Meta- Ortho- Para- V mononitromononitfomononltro Freezingpoint.

toluene. toluene. toluene.

Parts. Parts. Parts.

45 5 @3 so as 15 27". 60 36 4 Muddy, very thick. 60 24 16 Do. LD 60 4 36 25.

so 2 1s Hallsolid,ha1lliquid. 8O 6 14 '1t02. so 10 -1= m-r. so 12 '8 .-1 to -2. so 14 6 1. 90 is 2 0 l 2. Production of supernitrated liquid derivatives; that is to say, those with the proportion of mtrogen comprised between 15.3 and 16 per cent., (Series II). (a)-D1ssolv1ng .sohd trmitro-toluene in liquid binitro-toluenes of Series I. (The solid trinitro-toluene used is the commercial product melting at from 72 to 74 'C. -The results are the same with para-trinitrotoluene melting at 82 0.).

Order I- Io of Quantity Proporbmltromums of of blmtrotron ol Melting point.- stoluenle Seriesl toluene. mtrogen erles 0 1 Pans. Parts. Per cent; 95 5 15.5 -4.

85 15.8 11., 75 25 16.0 -24": becomes muddy about '18. -70 30 16.2 Solid at ordinary tom- 5 perature. 2 95 5 15.5 -5.

85 15 15.8 13. 75 25 16.0 -23: becomes muddy about 70 30 16.2 Solid at ordinary temperature. 3 95 5' 15.5

.85 15 15. 8 13 to 14. 0 7 so 2o a 15.9 -l7to -1s.

75' 16.0 -26; becomes muddy about 1(l. 70 30 16.2 Solid at ordinary temperatures. 4 95 5 15.5

1 75 25 16.0 Has no sharply define 5 melting point; becomes 1 I muddy about 5. 70 I 30 16.2 Solid at ordinary temperature.

5 '9' 5 15.5 Eel! solld halfliquid.

85 15 15.8 -Uncertaln: melting (point notsharpl define ,becomes mu dy about 5.

75 25 16.0 D0. 0 70 30 m2 Solid at ordinary temperature.

(b) Nitration of Series I, then dissolv in the product thus obtained. 5 his method is not described herein, for the reason that it is more complicated than the preceding one. (a) Direct nitration, by means of the ordinary nitrating mixture, of a-mixture of 0 meta-mononitro-toluene and of solid trinitrotoluene with either ortho-mononitro-toluene,

or with 'para-mononitro-toluene,-or with a mixture of both.v Only one example will be given, owing to the complexity of this method. As, a starting point is taken a mixture of 60 parts of meta-mononitro-toluone and of 40 parts of ortho-mononitroto1nene,-fo r example, No. 3 of the Series I, and in the same is dissolved commercial trinitrostoluenee Mixture No. 3 of metamononitro toluene and ortho mononitrotoluene, 77 parts; trinitro-toluene, 23 parts; proportion of nitrogen after nitration, 15.8%; freezing point, 16 to 17.

(03) Nitration, by means of a greater quantity of nitrati'ng mixture, with heating .to 90, of a mixture of meta-mononitrotoluene or either ortho-mononitro-toluene,

or with para-mononitro-toluene, or both.

. It is possible to use, for instance a mixture of parts of meta-mononitro-toluene and 40 parts of ortho-mononitro-toluene,

and to nitrate the same with one and a half the quantity of nitrating mixture that would have been necessary for obtaining the exactly binitrated product. The first stage of nitration is carried out at'a temperature of 60, then itis raised to and maintained for an hour to an hour and a half. The product obtained, after washing and neutralization, is liquid. Its proportion of nitrogen is 15.9%, its freezing point is -18, and it has the same properties as those prepared in accordance with (b).

The new products obtained according to this invention can be used for any purposes in which the so-called commercial liquid trinitro-toluene, is used, and they are especially Well adapted for the manufacture of of meta-mononitro-toluene, to obtain a liquid binitro-toluene; and dissolving in said binitro-toluene solid trinitro-toluene.

3. The process of producing liquid nitro-. toluene compounds which consists in nitrating a mixture of mononitro-toluenes containing essentially from 45 to 85 er cent.

of meta-mononitro-toluene to obtain a liquid binitro-toluene; nitrating said binitrotoluene; and mixing the resultant trinitrotoluene with liquid binitro-toluene.

4. The liquid nitro-toluene compounds obtained by mtrating mixtures of mononitrotoluene containing essentially from 45 to 85' per cent. .of meta-mononitro-toluene, said compounds being true liquids havin sharply-defined, constant melting points and characterized by their freedom from mononitro dei i vatives and from loss of weight specification in the presence of two subwhen heated for a period of twenty-four scribingwitnesses. hours to 60 0., and by the quantity of 'JULES MAIRE. nitrogen which they contain remaining the Witnesses:

5 same before and after such heating. EMILE LEDRET,

Intestimony whereof I have signed ibis LUCIEN MEMMINGER. 

